Azo dyestuffs and material dyed therewith



Patented May 13, 1930 UNITED STATES PATENT OFFICE 0F SODENON-THE-TAUNUS, ANl) ADOLI; KUCHENBECkER AND RICHARD HUSS, OF FRANKFORT-ON-THE-MAIN-HOCHST, GERMANY, ASSIGNORS '10 GENERAL ANILTNE WORKS, INC., OF NEW YORK, N. Y., A. CORPORATION OF DELA- WARE Ho Drawing. Application filed December 3, 1928, Serial No. 323,557, and in Germany December 18, 1927.

The present invention relates to new azo dyestuffs and material dyed therewith.

We have found that dyestuffs of violet tints are obtain-ed by coupling a diazo compound of the till present unknown di-ethers of 1 amino-2.4-dioxy-5-aroylaminobenzene of the following formula:

R1 wherein R and R stand aralkyl and wherein the aroyl residue may besubstituted or not, butmay not contain any free sulfonic acid or carboxyhc acid group, with a 2.3-hydroxynaphthoic acid arylami'de.

The dyestufl's are distinguished by an excellent fastness to washing and chlorine and partially by very good fastness to kier-boilmg. They are suitable for the roduction of dyeings on animal and vegetale fiber and on viscose silk. The tints vary between red violet and blue violet. r The dyestuffs may be prepared on the fiber and in substance. 7 The following examples serve to illustrate our invention but they are not intended to limit it thereto.

In the Examples 1-3 and 8'11 regarding dyeing cotton yarn there are lmpregnated grams of bleached cotton yarn with the 1. (a) Grounding liquor 0.4 gram of 2.3-hydro aphthoic acid-5-chloro 2-toluidide 0.8 cc. of Turkey oil of 50 r cent strength 1 cc. of caustic soda lye of 3 B6. are dissolved to- 1 m gether and made up with water to for alkyl, aryl or .AZO DYEST'O'FFS ANDMA'IERIAL DYED THEBEWITE 1 The dyeing is a vivid violet fast to boiling 2. (a) Grmmding liquor 1.1 gramof 2.3-hydroxynaphthoic acid-ortho-toluidide 2.2 cc. of Turkey red oil of 50 er cent strength 1.7-cc. of caustic soda lye o! 3 36. are dissolved tom gether and made up with water to.

' (b). Dye-bath 1 gram of -1 amino 2.4-dimethoxy-5-benzoylaminobenzene is diazotized with 1 cc. of hydrochloric acid of 22 B. and

3 cc. of sodium nitrite 1:10, while cooling with ice.

When diazotization is complete the liquid is neutralized with about 4 cc. of sodium acetate solution 1:5 and 2 cc. of sodium bicarbonate solution 1:10, whereupon 10 grams of common salt are added and the whole is n made up with water to 1 er v There is obtained boiling lye.

I 5. (a) Grounding liquor 0.63 grain of 2.3-?lygroxynaphthoic acid-2'.5-dimethoxy- 1.26 cc. of Turkey red oil of 50 per cent strength, and

126 cc. of caustic soda lye of 34" B., are dissolved together and made up with water to '1 liter 1 (b) Dye-bath 1 gram of 1-amino-2.4-dimethoxy 5-benzoylaminobenzene is diazotized with 1 cc. of hydrochloric acid of 22 Be. and 3 cc. of sodium nitrite 1:10, while cooling with ice.

When. diazotization is complete, the liquid is neutralized with about 4 cc. of sodium acetate solution 1 :5 and 2 cc. of sodium bicarbonate solution 1 :10, whereupon 10 grams of common salt are-added andthe whole is made up with water to 1 liter There is obtained a dull violet of good properties of fastness. .7

a vivid violet fast to (a) Grounding liquor 0.45 am of .2.3-h.ydroxynaphthoic acid-meta-nitrsnilide 0.9 of Turkey red oil of 50 per cent strength and 1.35 cc of caustic soda lye of 34 B. are dissolved 00 together and made up with water to The solution is cooled and mixed 'with 0.45 cc. of formaldehyde of 30 per cent strength. To this solution there is added a small quantity of a protective colloid and the whole is made up to 1 liter. 33 grams of degummed chappe silk are treated for 20 minutes in this grounding-bath and then there are added to the liquor 10 grams of common salt and the treatment is continued for .another 20 minutes. The yarn is then drained by centrifuging and. dyed for 20 minutes in the following bath.

' (b) Dye-bath 1 gram of 1-amino;2.4-dimethoxy-fi-beuroylaminobenlene is diazotized and then neutralized in the manner described in Example 1!). To the solution thus obtained is added of acetic acid of 50 per cent strength and the whole is made up withrwater to 1 liter .The yarn. I is well rinsed, then passed through a warm bath containing 3 cc. of hydrochloric acid of 22 B. per litre. After further rinsing, the yarn is then passed through a warm sodium carbonate bath conacid-5-chloro-2-toluidide for the 2.3-hy-' 'droxynaphthoic acid-meta-nitranilide. The

dyeing obtained is a vivid violet fast to boilmg.

6. In this case the procedure is as in Example 40: with use of 2.3-hydroxynaphthoie acid-ortho-toluidide instead of 2.3-hydroxynaphthoic acid-meta-nitranilide, the roportions being the same. The dyeing o tained is a vivid violet fast to boiling.

7. 272 parts of l-amino-2A-dimethoxy-5- benzoylaminobenzene are diazotized by means of 69 parts of sodium nitrite in hydrochloric acid in the usual .manrfer, and the. diazo-' solution is coupled with. an alkaline solu v tion of 2.3-hydroxynaphthoic" acid-5-chloro-2-toluidide (NH: Cl:CH =1:-4:6 "The violet preci itate thus obtained-isffiltered,";

washedand 'ed.

I 8. I I

4 gram of 2.3-hydroxynaphthoic acid-IS-chloro-2-toluidide 8 cc. of Turkey-red oil of 5051a cent strength and cc. of caustic loda lye of B6. are dissolved togather and made up with water to l 3.6 grams (b) Dye-bath 1 gram of 1-amino-2.4-dimethoxy-56benzoylaminobenzene is diazotized by means 0 1 cc. of hydrochloric acid of 22 Be. and 3 cc. of sodium nitrite (1 :10) while cooling with ice. When diazotization is finished there are added 20 cc. of sodium bicarbonate solution (1:10) and 10 grams of common salt,-and the whole is made up with water to e 1 liter The dyeing obtained is a vivid violet, fast to boiling lye.

.9. (a) Grounding liquor 1.1 grams of 2.3-hydroxynaphthoic acid-ortho-toluidide- 2.2 cc. of Turkey red oil of 50 per cent strength and 1.7 cc. of caustic soda lye of 34 36. are dissolved together and made up with water to 1 liter (b) Dye-bath 1 gram of 1-amino-2.4-dimethoxy-5benzoylaminobenzene is diazotized with 1 cc. of hydrochloric acid of 22 Be. and 3 cc. of sodium nitrite (1 :10) while cooling with ice.

- When diazotization is complete the li uid is neutralized with 20 cc. of sodium bicar nate solution (1 :10), whereupon 10 grams of common salt are added and the whole is made 1 m up with water to The dyeing obtained is a vivid violet fast to boiling lye.

10. (a) Grounding liquor 1.63 grams of 2.3-hydroxynaphthoic acid-2'.5'-dimethoxyl-anilide 1.26 cc. of Turke red oil of 50 per cent strength v 1.26 cc. of caust c soda lye of 34 Be. are dissolved I-fi-fg together and made up with water to (b) Dye bath 1 gramof 1-amlno-2.4-dimethoxy-5-benzoylamiuobenzene is diazotized by means 0 :1 cc. of hydrochloric acid of 22 BJand When diazotization is finished there are added 20 cc. of sodium bicarbonate solution (1 :10), i whereupon 10 grams of common salt are added and the whole is made 1 lit up with water to 'The dyeing obtained a dull violet of good properties of fastness.

11. (a) Grounding liquor o! 2I3-hydroxynaphthoic acid-5-chloro-2-toluidide 0t Turkay red oil of '50 pgr cent strength and 7.2 cc. of cans c soda lye of Be. are dissolved together mixed with 3.6 cc. of formaldehyde 0t 30 per cent strength and made up with water to v Q) 1 liter I (b) Dye-beth 2.85 grams of l-amino-2.4-diethoxy-5-benzoylaminobenzen are diazotized with 5.2 cc. of hydrochlorlc'acid of 22 B. and 15 cc. of sodium nitrite (1:10) while cooling with ice. en diazotization is complete, the liquid is neutralized with about cc. oi. sodium bicarbonate (1:10) and 25 m of common salt are added and the whole is made 1 at up' withwater to There is obtained a very deep vivid violet fast to boiling lye. The coupling on vegetable fiber is particularly rapid and complete'if as in the Examples 8-11 the operation isiconducted in alkaline or bicarbonate solution. The dyeings of sodium nitrite (1:10) while cooling with ice.

obtained are more powerful than when the coupling is in acetic acid.

A series of further valuable dyestuffs obtainable on the fiber according to the invention are as follows:

2.3'-hydroxynaphthoic acid-2-ani8idide 2'.3'-hydroxynaphthoic acld-4-anisldide 2'.3-h ydroxynaphthoic acid-l-naphthylamide 2.3'-hydroxynaphthoic acid-2-naphthylam'ide 2.3'-hydroxynaphthoi0 acid-anilide 2'.3-hydroxynaphtho'lc acid-3-nitranilide 2. 3'-hydroxynaplithoic acid-dianisidide 2'.3' -hydroxynaphthoic acid condensed with 2-aminodiphenyl ether 2'.3-hydroxynaphthoic acid-4chloro-2-anlsidlde 2'.3'-hydroxynaphthoic acid-2chloranilide I 2'.3'-hydroxynaphthoic acid-3-chloranilide 2.3-hydroxynaphthoic acid-4-chloranllide 2'.3'-hydroxynaphthoic 'acid --toluidide 2.3'-hydroxynaphthoic acid5-chIoro-Z-anisidide 2'.3-hydroxynaphthoic aCid-Z-toluidide 2'.3'-hydroxynaphthoic acid-2-anisidide 2'.3'-hydroxynaphthoic acid condensed with aminohydroquinone-dimethyl-ether 2.3'-hydroxynaphthoic acid-l-naphthylnmide 2'.3'-hydroxynaphthoic acid-2-naphthylamide '.3'-hydroxynaphthoic :1cid-4-aiiis;id.itle

2.3-hydroxynaphthoic acid-3-nitranilide 2'.3-hydroxynaphthoic acid-3-nitranilide 2.3'-hydroxynaphthoic acid-2-toluidide We claim: 1. .As new products, azo dyestufis of the following formula:

N=N 0 R1 N-aroyl C 0NH-aryl wherein R and R stand for alkyl, aryl or aralkyl and wherein the aroyl residue and the aryl residue may be substituted or not, but

may not contain any free sulfonic acid or carboxylic acid group, being reddish-violet to bluish-violet dyestufi's Insoluble 1n water.

2. As new products, azo dyestuffs of the "following formula:

03 zNn-co x v with with wherein R and R stand for alkyl, arylor aralkyl and X stands for hydrogen, or any substituent with the exception of a free sulfonic acid or carboxylic acid group and wherein the aryl residue may be substituted with with with

with

with

with

with

with

with with with with

with

with

with

with

1-amin0-2.4-dimethoxy-5-benzoylaminobenzene Bed violet v 1-amino-2.4dlmethoxy-5-benzoylaminobenzene Red violet 1-amino-2.4-dimethoxy-S-benzoylamlnobentene Bluish violet l-amin0-2.4-dimethoxy-5-benzoylaminobennene Bluish violet l-amino-2.4-dimethoxy-5-benzoylaminobenzene Bluish violet 1-amino-2A-dimethoxy-5-benzoylaminobenzene Vivid violet 1-amino-2.4-dimethoxy-5-benzoylaminobenzene Currant #:upino-Ll-dimethoxy-5-benzoyiaminobenzehe 0 ,et 1-amino-2.441imethoxy-5-benzoylaminobenzene Red violet 1-:1mine-2.4-dimethoxy-5-benzoylaminobenzene vivid bluish violet 1'-amino-2.4 dimethoxy-5-benzoy1amlnobenzene Vivid violet 1-amino-2.4-dimethoxy-5-benzoylaminobenzene Reddish violet l-amino-2.4 dimethoxy-S-benzoylaminobenaene Vivid reddish violet 1-amine-2.4-diethoxy-5-benzoylaminobenzene Vivid violet 1-amin0-2.4-diethoxy-5benzoylaminobenzene Vivid bluish-violet Lamino-2.4-diethoxy-5-benzoylaminobenzene Red violet 1-amino-2.441iethoxy-5-benzoylaminobenzene Red violet with 1amino-2.4-diethoxy-5-benzoylaminobenzene with with

with

lv inpinoQA-diethoxyfi henzoyiaminobenzene o e ifaxplpoa.4 diethoxy-5-benzoylaminobenzene 10 e 1-a1nino-2.4-diethoxy-5-benzoylaminobenzene Vivid violet inobenzene Vivid violet with 1-amino-2.4-dlmethoxy-5-(parachlorbenzoyl) aminobenze e Vivid violet with dibenzylether of 1-amino-2.4-dihydroxy-5-benzoyiamino benzene Reddish-violct with dibenzylether of l-amino-Z.4-dihydroxy-5-benzoylamino benzene Reddish-violet with dibenzylether of 1-amin0-2.4-dihydroxy-5benzoylhm- 'ino benzene Reddish-violet or not, but may not contain a free sulfonic acid or carboxylic acid group, being reddishviolet to bluish-violet dyestuffs, insoluble in water.

3. As new products, azo dyestufis of the following formula:

wherein R and R stand for alkyl, aryl or araikyl and X stands for hydrogen, alkyl or halogen and wherein the aryl residue may be substituted or not, but may not contain a free sulfonic acid or carboxylic acid group, being reddish-violet to bluish-violet dye stuiis,insoluble in water.

1 amino 2.4-dimethoxy-5-(para-methoxybenzoynam- 4. As new products, azo dyestufisof the following formula: 5

0H NH-C 0-42.11-

wherein R and R stand for alkyl, aryl or aralkyl and wherein the aryl residue maybe substituted or not, but may not contain a I free sulfonic acid or carboxylic acid group,

being reddish-violet to bluish-violet dyestuffs, insoluble in water. 5. As new products, azo dyestuffs of the following formula:

OH NH-aroyl CO-NH-ary] wherein the aroyl residue and aryl residue may be substituted or not, but may contain no free sulfonic acid or carboxylic acid group, being reddish-violet to bluish-violet dyestufis, insoluble in water.

6. As new products, azo dyestuffs of the following formula:

wherein X stands for hydrogen or any substituent with'the exception of a free sulfoor carboxyl group and wherein the aryl residue may be substituted or not, but may not contain a free sulfonic acid or carboxylic acid group, being reddish-violet to bluish-violet dyestuffs, insoluble in water.

halogen and wherein the aryl residue may be substituted or not, but may not contain a free sulfonic acid or carboxylic-acid group, being reddish-violet to bluish-violet dyestuffs, in- 05 soluble in water.

8., As new products, azo dyestufl's of the following formula:

OOH: N=N-Q-0GH; Nn-co-cm.

v 0-NH-aryl wherein the aryl residue may be substituted or not, but may not contain a free sulfonic acid or carboxylic acid group, being reddishviolet to bluish-violet dyestuffs, insoluble in water. r

9. As new products, azo dyestuflsfof the following formula:

oon,

N.=N oon.

0H vmer-co-o-m 4 OONHR being a fast violet dyestufi, insoluble in water.

claimed in claim 9.

20. Material dyed with the dyestufl as claimed in claim 10.

In testimony whereof, we aflix our signatures.

HERMANN WAGNER. ADOLF KUCHENBECKER. RICHARD HUSS.

- 11. Material dyed with dyestuffs as claimed in claim 1. I

12. Material dyed with dyestuffs as claimed in claim 2.

13. Material dyed with dyestuffs as claimed in claim 3.

14. Material' dyed with dyestuffs as claimed in claim 4.

15. Material .dyed with 'dyestufls as claimed in claim 5. I

' 16. Material dyed with dyestuffs as claimed in claim 6.

17. Material dyed with dyestuffs as claimed in claim 7.

18. Material dyed with dyestuffs as claimed in claim 8. p v

19. Material dyed with dyestuffs as 50 7. As new products, azo dyestuffs of the following formula:

ocm' r N= Q0011. 55 n NH-coOX co-Nn m I wherein X stands for hydrogen, -OCH, or 

